EP0066241A2 - Modifizierter cis-1,4-Polyisopren-Kautschuk, Verfahren zu seiner Herstellung, Mischung von vulkanisiertem und modifiziertem cis-1,4-Polyisopren-Kautschuk und Verwendung von modifiziertem cis-1,4-Polyisopren-Kautschuk zur Herstellung von Formteilen - Google Patents

Modifizierter cis-1,4-Polyisopren-Kautschuk, Verfahren zu seiner Herstellung, Mischung von vulkanisiertem und modifiziertem cis-1,4-Polyisopren-Kautschuk und Verwendung von modifiziertem cis-1,4-Polyisopren-Kautschuk zur Herstellung von Formteilen Download PDF

Info

Publication number
EP0066241A2
EP0066241A2 EP82104564A EP82104564A EP0066241A2 EP 0066241 A2 EP0066241 A2 EP 0066241A2 EP 82104564 A EP82104564 A EP 82104564A EP 82104564 A EP82104564 A EP 82104564A EP 0066241 A2 EP0066241 A2 EP 0066241A2
Authority
EP
European Patent Office
Prior art keywords
rubber
modified
polyisoprene rubber
residue
carbon atoms
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP82104564A
Other languages
English (en)
French (fr)
Other versions
EP0066241B1 (de
EP0066241A3 (en
Inventor
Hideo Takamatsu
Shobu Minatono
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kuraray Co Ltd
Original Assignee
Kuraray Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kuraray Co Ltd filed Critical Kuraray Co Ltd
Publication of EP0066241A2 publication Critical patent/EP0066241A2/de
Publication of EP0066241A3 publication Critical patent/EP0066241A3/en
Application granted granted Critical
Publication of EP0066241B1 publication Critical patent/EP0066241B1/de
Expired legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
    • C08C19/34—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with oxygen or oxygen-containing groups
    • C08C19/36—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with oxygen or oxygen-containing groups with carboxy radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/28—Reaction with compounds containing carbon-to-carbon unsaturated bonds

Definitions

  • This invention relates to a modified cis-1,4- polyisoprene rubber. More particularly, it is concerned with a solid synthetic cis-1,4-polyisoprene rubber modified by incorporation of succinimide residues carrying at the imide nitrogen a hydrocarbon group containing a tertiary amino group.
  • Synthetic cis-1,4-polyisoprene rubber (according to A STM nomenclature hereinafter referred to as IR) has a molecular structure which is similar to that of natural rubber .(according to ASTM nomenclature hereinafter referred to as NR).
  • IR is closer to NR in its properties than any other synthetic rubber. It has very good workability, and the.vulcanized products have excellent physical properties. It is a general-purpose rubber which is used as a substitute for N R in the manufacture of automobile types, industrial rubber products, rubber footwear, and the like.
  • IR is a synthetic polymer, it contains impurities and foreign matter in much smaller quantities than N R. This feature is of considerable importance, since it reduces the possibility of the production of rejects. This is one of the outstanding features of IR which has created a great demand for IR in certain fields of applications.
  • IR is, however, considerably inferior to NR in green strength. Accordingly, IR will show cold flow during storage, and various kinds of trouble are likely to occur during the manufacture of rubber products as will hereinafter be pointed out.
  • unvulcanized rubber compositions are put together and molded to form a tyre, they are likely to undergo sagging or change in their physical properties, or the tyre cords embedded in the unvulcanized materials are likely to get displaced, resulting in failure to provide uniform types.
  • the low green strength of IR however, means good flowability. It is, therefore, one reason to blend IR with NR despite some reduction in its green strength.
  • Japanese Laid-Open Patent Specification No. 102148/73 proposes the incorporation into synthetic rubber, such as IR, of a maleic acid amide of the general formula where R stands for a hydrogen atom, or an alkyl, phenyl, chlorophenyl, nitrophenyl, benzyl, formylaminophenyl or cyclohexyl group, or a derivative of maleamide, or malein- hydrazide in order to improve its green strength without lowering the physical properties of its vulcanizate.
  • R stands for a hydrogen atom, or an alkyl, phenyl, chlorophenyl, nitrophenyl, benzyl, formylaminophenyl or cyclohexyl group, or a derivative of maleamide, or malein- hydrazide in order to improve its green strength without lowering the physical properties of its vulcanizate.
  • EXAMPLE 1 shown therein indicates certain improvements in the green strength of synthetic rubber at ordinary room temperature, and the strength and modulus of its vulcanizate, but simultaneously suggests the necessity for improvement in flowability and workability at elevated temperatures, since the tensile strength of the uncured.compound measured at 80°C was as high as, or even higher than that of NR which is at least 1.6 times higher than that of IR.
  • Japanese Laid-Open Patent Specification No. 45198/76 proposes that an amine, such as an amino alcohol or polyethyleneimine having at least three amino groups, be incorporated into modified IR containing maleic anhydride.
  • an amino alcohol improves the green strength of the modified IR, it is not so high as that of NR, and the tensile strength and hardness of its vulcanizate are not so high as those of NR.
  • polyethyleneimine does not improve the flowability of the modified IR at elevated temperatures;in other words, its tensile strength at elevated temperatures is not so low as that of IR.
  • the principal object of this invention is therefore to provide a novel modified cis-1,4-polyisoprene rubber which is excellent in green strength and flowability at elevated temperatures, and its vulcanizate is comparable to, or better than NR in tensile strength and hardness.
  • This invention improves the drawbacks of IR and modified IR which have hereinabove been pointed out.
  • tensile strength means tensile strength at break.
  • a modified cis-1,4-polyisoprene rubber on the basis of a solid synthetic cis-1,4-polyisoprene rubber containing per 100 repeating isoprene units as a side chain at least 0.01 mole of a functional group of the general formula wherein R 1 is hydrogen or a covalent bond with the rubber molecule, R 2 is a hydrocarbon residue ha.ing not more than 20 carbon atoms, and optionally containing oxygen or sulfur in its principal chain, and A is a dihydrocarbylamino residue having not more than 20 carbon atoms, or a heterocyclic residue containing at least one tertiary nitrogen atom as a hetero nitrogen atom.
  • the heterocyclic residue may contain one or more further hetero atoms, such as nitrogen, oxygen or sulfur atoms, in addition to the tertiary nitrogen atom.
  • modified rubber of this invention can be vulcanized at a rate which is equal to, or higher than the vulcanization rate of NR:
  • the modified rubber of this invention can be manufactured by two methods:
  • a solid synthetic cis-l,4-polyisoprene rubber(IR) obtained by polymerizing isoprene with a Ziegler or anionic catalyst, and having a cis-1,4 content of at least 80%.
  • IR cis-1,4-polyisoprene rubber
  • high cis-1,4-polyisoprene rubber obtained with a Ziegler catalyst and having a cis-1,4 content of at least 95%.
  • a rubber having any molecular weight if it is a solid, but it is preferable to use a rubber having a molecular weight of 200,000 to 2,000,000.
  • the amine used for the preparation of the modified cis-1,4-polyisoprene rubber of this invention by the first method above described has the general formula II H 2 N-R 2 -A, in which R 2 is a divalent hydrocarbon residue having not more than 20 carbon atoms and optionally containing an oxygen or a sulfur atom in its principal (main) chain.
  • the preferred group R 2 is
  • A may, for example, stand for:
  • R 2 and A residues having not more than 20 carbon atoms, and more preferably 2 to 12 carbon atoms each.
  • Typical examples of the amines which may be used for this invention include (dialkylamino)alkylamines (N,N-dialkylaminoalkoxy)alkylamines,aminesobtained by substitution of poly(oxyalkylene)for alkoxy in the (N,N-dialkylaminoalkoxy)-alkylamine mentioned above, p-N,N-dialkylaminomethyl- benzylamines,p-N,N-dialkylaminophenylamines,N-aminoalkyl- piperidines,N-aminoalkyl-pipecolines,N-aminoalkyl-morpholines, 1-aminoalkyl-4-alkyl-piperazines, aminoalkyl pyridines,and picolylamines.
  • dialkylamino alkylamines having a (dialkylamino) alkyl residue substituted for hydrogen in an alkylene residue between the nitrogen atoms. It is particularly preferred to use (dialkylamino)alkylamines, such as (dimethylamino)ethylamine, (diethylamino)ethylamine, (dipropylamino)ethylamine, (dimethylamino)propylamine, (diethylamino)propylamine, (dimethylamino)butylamine, (di- ethylamino)butylamine, (dimethylamino)hexylamine or (dimethyl- amino)decylamine, or (N,N-dialkylamino)alkoxyalkylamines,such as (N,N-dimethylamino)ethoxyethylamine, (N,N-dimethylamino) eth
  • the maleimide derivative used as a modifying agent for the manufacture of the modified IR of this invention by the second method above described has the general formula (III) in which R 2 and A are as hereinbefore defined. It is particularly preferred to use a N -(dialkylamino)alkylmaleimide, such as N-( ⁇ -dimethylamino) ethylmaleimide, N-(B-diethylamino)ethylmaleimide, N-(y-dimethylamino)propylmaleimide, N-(y-diethylamino)propyl- maleimide, N-( ⁇ -dimethylamino)butylmaleimide, or N-(6-di- ethylamino)butylmaleimide.
  • N -(dialkylamino)alkylmaleimide such as N-( ⁇ -dimethylamino) ethylmaleimide, N-(B-diethylamino)eth
  • IR Maleic anhydride, maleic acid, a maleic acid monoester a or diester, or a maleic acid derivative, such as a maleimide of the general formula (III), is added to IR in the form of absolution or in a solid state.
  • IR is dissolved in a solvent, such as an aliphatic, alicyclic or aromatic hydrocarbon, a maleic acid derivative, for example, is added to the solution, and the solution is heated optionally in the presence of a free radical forming agent, such as a peroxide or azo compound.
  • the mixture is usually heated at a temperature of 25°C to 250°C, preferably 50°C to 200°C, for a period of 0.1 minute to 100 hours, preferably 0.5 to 30 hours.
  • a maleic acid derivative for example, is mixed with IR by using a roll mill, kneader, Banbury mixer, screw extruder, or the like.
  • the reaction may be performed in the presence of a catalyst or free radical forming agent, such as a peroxide or azo compound, though it often does not require any such catalyst.
  • the reaction is usually performed at a temperature of 25°C to 300°C, preferably 50°C to 250°C, for a period of 0.1 minute to 100 hours, preferably 0.5 minute to 30 hours.
  • the quantity of the maleic acid derivative in the I R is preferably in the range of 0.01 to 10 moles, aggregateularly 0.01 to 2 moles, and more preferably 0.05 to 1.0 mole, per 100 repeating isoprene units in the IR:
  • the modified IR obtained by adding maleic anhydride, maleic acid, or a maleic ester is then reacted with an amine of the general formula (II) at a temperature of 0° to 150°C. for a period of 0. 1 minute to 20 hours.
  • the acid anhydride or carboxyl groups are converted into amide groups which are then converted to cyclic amide groups by a denydration or dealcoholization reaction. If the reaction is not complete, some monosuccinamidecarboxylic acid is likely to remain in the product. If its quantity is small, there is no problem, but if it is large, there is the likelihood that the properties claimed to be obtained by this invention may not be obtained. It is, therefore, preferred to heat or otherwise treat the product so that the monosuccinamidecarboxylic acid groups are converted to imide groups.
  • the modified IR of this invention is excellent in green strength, workability at elevated temperatures, rate of vulcanization, and its vulcanizate exhibits very good physical properties. Therefore, it is useful not only for those applications for which IR has hitherto been used, i.e. as general purpose rubber, but for other applications as well.
  • compounding agents employed-ordinarily for the manufacture of finished rubber products.
  • the compounding agents include a reinforcing agent(5 - 200 phr), such as carbon black(soft or hard), or calcium carbonate, a filler(5 - 200 phr), a vulcanizing agent (0.1 - 10 phr), such as sulfur or a peroxide, an auxiliary vulcanization accelerator (0.01 - 7 phr), an antioxidant (0.05-5 p hr ) , a softener .(1 -40 phr), such as an oil, and a resin (1 - 200 phr), such as rosin, a terpene, petroleum phenol, epoxy, polyester or polyamide resin.
  • Examples of rubber constituents include natural rubber, untreated IR, styrenebutadiene rubber, polybutadiene rubber and other synthetic rubbers, and in some cases, mixtures thereof with a liquid polyisoprene or polybutadiene.
  • modified IR of this invention is mixed with unmodified IR, it is important to ensure that the modified IR and the unmodified IR have a weight ratio of 5:95 to 95:5, and that the mixture contains 0.01 to 2.0 mole % of the compound of the general formula I or II.
  • the modified IR of this invention may advantageously be employed to manufacture various parts of an automobile tyre, such as treads, carcasses, beads, bead fillers or rim strips,industrial products such as V-belts, hoses, vibration insulators or rubber rolls, rubber-coated fabrics, rubber shoes, rubber threads, rubber rings, sponge rubber articles, and the like.
  • Synthetic cis-l,4-polyisoprene rubber prepared with a Ziegler catalyst, and having a cis-1,4 content of 98% and a molecular weight of 840,000 (Kuraprene IR-10; product of KURARAY ISOPRENE CHEMICAL CO., LTD., Japan) was dissolved in toluene to form a 10% IR solution.
  • Maleic anhydride was added to the solution so that it contains 2.5 parts of maleic anhydride per 100 parts of IR.
  • the solution was heated at 180°C. for five hours to yield a solution of IR modified with maleic anhydride.
  • the modified IR was recovered from the solution, and purified.
  • the reaction ratio of maleic anhydride was 12 %.
  • the total reflection spectrum of the modified IR was obtained at an incidence angle of 70° and by 20 times of integration by employing an infrared spectrophotometer(Digilab's FTS-20% Fourier transformation type).
  • the IR-spectrum obtained is shown in FIGURE 2, while FIGURE 1 shows the infrared spectrum of unmodified IR.
  • the peaks which are due to the carbonyls of the acid anhydride groups are found at 1,790 cm -1 and 1,870 cm -1 , and they confirmed the formation of the IR modified with maleic anhydride.
  • the quantity of the succinic anhydride residuesin the IR modified with maleic anhydride was 0.21 mole per 100 repeating isoprene units in the IR.
  • modified IR For comparison purposes, several other kinds of modified IR were likewise prepared by adding, instead of (dimethylamino)propylamine, an equal molar quantity of ethanolamine, di-n-propylamine, ethylenediamine, polyethyleneimine having a molecular weight of 1,200 (PEI SP-012, product of NIPPON SHOKUBAI KAGAKU KOGYO K.K., Japan) or N,N'-diphenyl-p-phenylenediamine (Antigen P, product of SUMITOMO CHEMICAL INDUSTRIAL CO., LTD., Japan) to the IR modified with maleic anhydride.
  • PEI SP-012 product of NIPPON SHOKUBAI KAGAKU KOGYO K.K., Japan
  • Antigen P product of SUMITOMO CHEMICAL INDUSTRIAL CO., LTD., Japan
  • Rubber compositions were prepared from the modified IR, unmodified IR and NR in accordance with the recipe shown in TABLE 1. Strips having a thickness of 2 mm and a width of 6 mm were prepared from the uncured rubber compo- yield point, sitions (unvulcanizates), and tested for tensile strength,/ 300% modulus (M 300 ) , tensile strength and elongation at break by an Instron tester at a pull rate of 50 mm/min. at 25°C and 100°C. The rubber compositions were press cured at 145°C for 30 minutes to form vulcanizates. The vulcanizates were similarly tested for M 300 , tensile strength, and elongation at break at 25°C. They were also tested for hardness and tear strength. The test results are shown in TABLE 2.
  • Modified IR containing N-(y-dimethylamino)propylsuccinimide residues was prepared in accordance with the procedure of EXAMPLE 1, except that 12 parts of maleic acid and 20 parts of (dimethylamino)propylamine were used.
  • the modified. IR contained 1.41 moles of succinimide residues per 100 repeating isoprene units in the IR.
  • a modified IR containing monomethyl succinate residues was prepared in accordance with the procedure of EXAMPLE 1, except that monomethyl maleate was used instead of maleic anhydride.- It contained 0.51 moles of monomethyl succinate residues per 100 repeating isoprene units in the IR.
  • Uncured rubber compositions having a Mooney viscosity of about 80 were prepared from each of those two types of modified IR, unmodified IR and NR in accordance with the recipe adopted in EXAMPLE 1.
  • the stress-strain characteristics of the uncured rubber compositions at 25°C and 100°C were examined in accordance with the procedures employed in EXAMPLE 1.
  • FIGURE 4 shows their stress-strain characteristics at 25°C
  • FIGURE 5 shows the same at 100°C.
  • the abscissa indicates strain, and the ordinate stress.
  • Curves A, B, NR and IR show the stress-strain characteristics of the uncured rubber compositions prepared from the modified IR containing N-( ⁇ -dimethylamino)propylsuccinimide residues(Mooney viscosity: 78), the modified IR containing monomethylsuccinate residues (Mooney viscosity: 79), natural rubber (Mooney viscosity: 81), and synthetic cis-l,4-polyisoprene rubber (Mooney viscosity: 80), respectively.
  • IR having a molecular weight of 570,000 was prepared by masticating the IR (IR-10) employed in EXAMPLE 1.
  • a modifying agent (I) ⁇ -(N,N-dimethylamino)decylamine, (II) dimethylaminoethoxy- ethylamine or (III) bis(y,y-dioctylamino)ethylpropylamine, was added to the modified IR in a quantity in excess of that of consumed maleic anhydride, and they were reacted at 160°C. under reduced pressure for three hours.
  • the infrared absorption spectra of the reaction products showed the absorptions due to the carbonyls of the succinimide residues at 1,700 cm -1 and 1,770 cm -1 , instead of the absorptions due to the carbonyls of the acid anhydride groupsat 1,790 cm -1 and 1,87 0 cm -1 .
  • the modified IR containing N-(dimethyl- amino)decylsuccinimide residues had been formed when the modifying agent (I) was used, the modified IR containing N-(dimethylaminoethoxy)ethylsuccinimide residues had been formed when the modifying agent (II) was used, and the modified IR containing N-(bis( ⁇ , ⁇ -dioctylamino)ethyl)propylsuccinimide residues had been formed when the modifying agent (III) was used.
  • the addition of the modifying agent (I), (II) or (III) to the modified IR containing succinic anhydride residues improved its tensile strength tensile at 25°C. and the/strength, 300% modulus and hardness of its vulcanizate at 25°C. to a level comparable to those of NR, and its strength of unvulcanizate at 100°C. and its extrusion properties were comparable to those of IR.
  • the products of EXAMPLE 1 were also examined for extrusion properties at 100°C. and tensile strength at 100°C. It was found that the product which was comparable to IR in tensile strength at 100°C.
  • N-(y-diethylamino)propyl- maleimide were added to, and reacted with synthetic cis-1,4-polyisoprene rubber prepared with a Ziegler catalyst, and having a cis-1,4 content of 98% and a molecular weight of 840,000(Kuraprene IR-10, product of KURARAY ISOPRENE CHEMICAL CO., LTD., Japan).
  • the components were first mixed at 100°C. for two minutes, and then kneaded at 220°C. for five minutes, with aBrabender Plasti-Corder.
  • a modified IR was prepared by employing maleic anhydride or maleimide instead of N-(y-diethylamino)propylmaleimide.
  • the quantity of such incorporated maleic anhydride or maleimide in the modified IR is also shown in TABLE 5.
  • Rubber compositions were prepared from the various types of modified IR, unmodified IR and NR shown in TABLE 5 by kneading in accordance with the recipes shown in TABLE 6.
  • the unvulcanized rubber compositions were press cured at 145°C for 30 minutes to form vulcanizates.
  • the unvulcanized rubber compositions were tested for yield point, 300% modulus (M 300 ), tensile strength and elongation at break at 25°C and l00°C in accordance with the procedures of EXAMPLE 1.
  • the vulcanizates were likewise tested for 300% modulus (M 300 ), tensile strength and elongation at break at 25°C. They were also tested for hardness and tear strength. The results are shown in TABLE 6:
  • Synthetic cis-l,4-polyisoprene rubber (Kuraprene IR -10 of KURARAY ISOPRENE CHEMICAL CO., LTD., Japan) was dissolved in toluene to form a 10% solution of IR.
  • N-(y-dimethylamino)propylmaleimide was added to, and reacted with the solution at 100°C. for five hours in the presence a of/catalyst(0.01% of benzoyl peroxide based on IR), whereby modified IR containing N-( ⁇ -dimethylamino)propyl- repeating succinimide residues in the quantity( mole per 100/isoprene units in IR) shown in TABLE 7 was obtained.
  • the rate of gelation in the modified IR was examined, and is shown in TABLE 7.
  • the quantity of gel was determined by the following method: 1 g of rubber was dissolved in 150cc. of toluene at room temperature. The mixture is shaken for 12 hours. Then insoluble matter is removed by filtration through a 200-mesh metal wire sieve. The soluble and the insoluble matter is weighed after vacuum drying.
  • modified IR For comparison purposes, four kinds of modified IR were prepared by employing maleic anhydride instead of N-( Y -dimethylamino)propylmaleimide.
  • the quantity of incorporated maleic anhydride(i.e. succinic anhydride residue) and the rate of gelation in these modified IR are shown in TABLE 7.
  • Rubber compositions were prepared from these modified IR in accordance with.the recipes shown in TABLE 6, and vulcanized in accordance with the procedure described in EXAMPLE 1.
  • the physical properties of the unvulcanized compositions and the vulcanizates thereof were examined in accordance with the procedure of EXAMPLE 1, and are shown in TABLE 8.
  • the modified IR's obtained by employing N-(y-dimethylamino)propylmaleimide Formulation Nos 9 and 10) were superior to the modified IR's prepared by using maleic anhydride(Formulation Nos. 11 and 12) in flowability of the unvulcanizate at elevated temperature (100°C.) and hardness, 300% modulus and tear strength of the vulcanizate.
EP82104564A 1981-05-26 1982-05-25 Modifizierter cis-1,4-Polyisopren-Kautschuk, Verfahren zu seiner Herstellung, Mischung von vulkanisiertem und modifiziertem cis-1,4-Polyisopren-Kautschuk und Verwendung von modifiziertem cis-1,4-Polyisopren-Kautschuk zur Herstellung von Formteilen Expired EP0066241B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP80641/81 1981-05-26
JP56080641A JPS57195105A (en) 1981-05-26 1981-05-26 Preparation of modified cis-1,4-polyisoprene rubber

Publications (3)

Publication Number Publication Date
EP0066241A2 true EP0066241A2 (de) 1982-12-08
EP0066241A3 EP0066241A3 (en) 1983-02-23
EP0066241B1 EP0066241B1 (de) 1985-05-08

Family

ID=13723989

Family Applications (1)

Application Number Title Priority Date Filing Date
EP82104564A Expired EP0066241B1 (de) 1981-05-26 1982-05-25 Modifizierter cis-1,4-Polyisopren-Kautschuk, Verfahren zu seiner Herstellung, Mischung von vulkanisiertem und modifiziertem cis-1,4-Polyisopren-Kautschuk und Verwendung von modifiziertem cis-1,4-Polyisopren-Kautschuk zur Herstellung von Formteilen

Country Status (4)

Country Link
US (1) US4446281A (de)
EP (1) EP0066241B1 (de)
JP (1) JPS57195105A (de)
DE (2) DE3263648D1 (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0556727A1 (de) * 1992-02-20 1993-08-25 Kuraray Co., Ltd. Dienpolymere mit funktionellen Gruppen und diese enthaltende Kautschukmischungen
CN113121725A (zh) * 2021-04-19 2021-07-16 四川大学 一种改性聚异戊二烯橡胶及其制备方法

Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4574140A (en) * 1983-06-27 1986-03-04 The Goodyear Tire & Rubber Company Green strength of elastomers
EP1173878B1 (de) * 1999-04-27 2011-04-06 Bio-Rad Laboratories, Inc. Probenhalter für ein gasphaseionenspektrometer
EP1099711B1 (de) * 1999-11-12 2006-03-29 JSR Corporation Modifiziertes Polymer eines konjugierten Diens, Verfahren zur Herstellung und dieses enthaltende Elastomerzusammensetzung
ES2660902T3 (es) * 2005-12-28 2018-03-26 Bridgestone Corporation Composición de caucho con buenas propiedades de tracción en húmedo y bajo contenido de aceite aromático
US7700673B2 (en) * 2006-12-22 2010-04-20 Bridgestone Corporation Reduced oil rubber compositions including N-substituted polyalkylene succinimide derivates and methods for preparing such compositions
US9090127B2 (en) 2007-12-31 2015-07-28 Bridgestone Corporation Metal soaps incorporated in rubber compositions and method for incorporating such soaps in rubber compositions
US20090283186A1 (en) * 2008-05-15 2009-11-19 Gabor Kaszas Rubber composition and pneumatic tire
US8613298B2 (en) * 2008-05-15 2013-12-24 The Goodyear Tire & Rubber Company Functionalized elastomers
JP2011526327A (ja) * 2008-06-26 2011-10-06 株式会社ブリヂストン 金属で官能化されたポリイソブチレン誘導体を含むゴム組成物及びかかる組成物の調製方法
US7906592B2 (en) * 2008-07-03 2011-03-15 Bridgestone Corporation Polymers functionalized with imide compounds containing a protected amino group
JP5438131B2 (ja) 2009-01-23 2014-03-12 株式会社ブリヂストン 保護されたアミノ基を含有するニトリル化合物で官能化されたポリマー
WO2010085631A2 (en) 2009-01-23 2010-07-29 Bridgestone Corporation Polymers functionalized with polycyano compounds
US8389609B2 (en) * 2009-07-01 2013-03-05 Bridgestone Corporation Multiple-acid-derived metal soaps incorporated in rubber compositions and method for incorporating such soaps in rubber compositions
US9803060B2 (en) * 2009-09-10 2017-10-31 Bridgestone Corporation Compositions and method for making hollow nanoparticles from metal soaps
US8338544B2 (en) * 2009-12-21 2012-12-25 Bridgestone Corporation Polymers functionalized with polyoxime compounds and methods for their manufacture
US8748531B2 (en) 2010-12-10 2014-06-10 Bridgestone Corporation Polymers functionalized with oxime compounds containing an acyl group
US8802755B2 (en) 2011-01-18 2014-08-12 Bridgestone Corporation Rubber compositions including metal phosphate esters
US8962766B2 (en) 2011-09-15 2015-02-24 Bridgestone Corporation Polymers functionalized with polyhydrazone compounds
JP5952702B2 (ja) * 2012-10-09 2016-07-13 住友化学株式会社 ゴム組成物の製造方法、加硫されたゴム組成物成形体、および防振材
EP2914654B1 (de) 2012-11-02 2017-05-31 Bridgestone Corporation Kautschukzusammensetzungen mit metallcarboxylaten und verfahren zur herstellung davon

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3965076A (en) * 1973-07-13 1976-06-22 Kuraray Co., Ltd. Process for the production of modified cis-14,-polyisoprene
FR2300108A1 (fr) * 1975-02-07 1976-09-03 Sumitomo Chemical Co Procede de production de resines formees d'un produit d'addition d'un pol
DE2838930B1 (de) * 1978-09-07 1979-10-25 Huels Chemische Werke Ag Waessriges Behandlungsmittel fuer Holz und Holzwerkstoffe und dessen Verwendung
DE2944082A1 (de) * 1978-11-01 1980-05-14 Nippon Oil Co Ltd Ueberzugszusammensetzung zur elektrolytischen abscheidung durch kathoden- ausfaellung

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3778418A (en) * 1970-09-24 1973-12-11 Y Nakayama Maleinization process
JPS5946522B2 (ja) * 1976-12-10 1984-11-13 日石三菱株式会社 水分散性塗膜形成物質の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3965076A (en) * 1973-07-13 1976-06-22 Kuraray Co., Ltd. Process for the production of modified cis-14,-polyisoprene
FR2300108A1 (fr) * 1975-02-07 1976-09-03 Sumitomo Chemical Co Procede de production de resines formees d'un produit d'addition d'un pol
DE2838930B1 (de) * 1978-09-07 1979-10-25 Huels Chemische Werke Ag Waessriges Behandlungsmittel fuer Holz und Holzwerkstoffe und dessen Verwendung
DE2944082A1 (de) * 1978-11-01 1980-05-14 Nippon Oil Co Ltd Ueberzugszusammensetzung zur elektrolytischen abscheidung durch kathoden- ausfaellung

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0556727A1 (de) * 1992-02-20 1993-08-25 Kuraray Co., Ltd. Dienpolymere mit funktionellen Gruppen und diese enthaltende Kautschukmischungen
CN113121725A (zh) * 2021-04-19 2021-07-16 四川大学 一种改性聚异戊二烯橡胶及其制备方法

Also Published As

Publication number Publication date
JPS57195105A (en) 1982-11-30
EP0066241B1 (de) 1985-05-08
US4446281A (en) 1984-05-01
DE66241T1 (de) 1983-09-01
DE3263648D1 (en) 1985-06-13
EP0066241A3 (en) 1983-02-23

Similar Documents

Publication Publication Date Title
EP0066241B1 (de) Modifizierter cis-1,4-Polyisopren-Kautschuk, Verfahren zu seiner Herstellung, Mischung von vulkanisiertem und modifiziertem cis-1,4-Polyisopren-Kautschuk und Verwendung von modifiziertem cis-1,4-Polyisopren-Kautschuk zur Herstellung von Formteilen
US3427366A (en) Hydrocarbon rubber and polyurethane prepared from a polyisocyanate and an hydroxy terminated diene polymer
US6372855B1 (en) Polymer containing isobutylene as repeating unit and rubber composition containing the same
US5753761A (en) Method of preparing trans polybutadiene blend for use in tires
JPH0768416B2 (ja) ゴム加硫剤の製造法
JPS6114266A (ja) カーボンブラツク製品及びそれを含有するゴム組成物
KR970005964B1 (ko) 중합체 합금
US4248758A (en) Crosslinked EPDM/thermoplastic elastomer blend
JP2000063570A (ja) 抗戻り物質を含むゴム組成物及びその成分を有するタイヤ。
JPS62218430A (ja) 非汚染性加硫エラストマ−組成物およびこの組成物からなる側壁を備えたタイヤ
US5137981A (en) Halogenated polybutadiene series elastomers, method of producing the same and rubber compositions for tire containing this elastomer
JPH0411501A (ja) 空気入りタイヤ
KR100705989B1 (ko) 고무 조성물 및 이의 제조방법
EP0357534A1 (de) Vulkanisiermittel für Kautschuk
JPH0158212B2 (de)
US4426480A (en) Organo siloxanes, method for the preparation thereof and polymeric compositions containing same
FR2508046A1 (fr) Procede de modification de caoutchouc de cis-1,4-polyisoprene
JP2002128960A (ja) ゴム用加硫剤およびそれを含むゴム組成物
JP3469376B2 (ja) ゴム組成物
JPS5996106A (ja) 加硫用ゴム素材の製造法
US20020188082A1 (en) Novel vulcanizing agent for diene-based rubber and rubber composition using the same
JPS5817482B2 (ja) 改質ゴム状タ−ポリマ−の製造方法
US3632549A (en) Process for the preparation of compositions of synthetic diene polymers having improved green strength and processability
US4133845A (en) Polysegment copolymers
JPS6248695B2 (de)

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): DE FR GB IT NL

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Designated state(s): DE FR GB IT NL

ITCL It: translation for ep claims filed

Representative=s name: JACOBACCI CASETTA & PERANI S.P.A.

TCNL Nl: translation of patent claims filed
17P Request for examination filed

Effective date: 19830321

EL Fr: translation of claims filed
DET De: translation of patent claims
ITF It: translation for a ep patent filed

Owner name: MODIANO & ASSOCIATI S.R.L.

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): DE FR GB IT NL

REF Corresponds to:

Ref document number: 3263648

Country of ref document: DE

Date of ref document: 19850613

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19890517

Year of fee payment: 8

ITTA It: last paid annual fee
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19890531

Year of fee payment: 8

Ref country code: GB

Payment date: 19890531

Year of fee payment: 8

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19900201

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19900525

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19901201

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
GBPC Gb: european patent ceased through non-payment of renewal fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19910131

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST